Phenols and phenolic resins

ABSTRACT

PHENOLS, PHENYL ETHERS, BISPHENOLS, DIETHERS, MIXED PHENOL ETHERS AND PHENOLIC RESINS ARE PREPARED BY REACTING A PHENOL WITH A NON-CONJUGATED OPEN-CHAIN ALIPHATIC OR CYCLOALIPHATIC POLYUNSATURATED HYDROCARBON.

United States Patent O US. Cl. 260-612 R 4 Claims ABSTRACT OF THEDISCLOSURE Phenols, phenyl ethers, bisphenols, diethers, mixed phenolethers and phenolic resins are prepared by reacting a phenol with anon-conjugated open-chain aliphatic or cycloaliphatic polyunsaturatedhydrocarbon.

CROSS-REFERENCE TO RELATED APPLICATIONS This is a division ofapplication Ser. No. 612,334, filed Jan. 30, 1967, and now Pat. No.3,539,646, which is a continuation-in-part of application Ser. No.276,147, filed Apr. 29, 1963 and now abandoned.

BACKGROUND OF THE INVENTION This invention relates to new phenols and tophenolic resins which may be prepared from the new phenols. The phenolicresins used by the modern plastics industry are prepared by the reactionof phenol with a carbonyl compound or derivative. In each case thephenol linking bridge contains one carbon atom and is considered to beinflexible.

New phenols and phenolic resins have now been discovered which providelonger carbon chain bridges between phenolic nuclei.

SUMMARY OF THE INVENTION In accordance with the invention there areprovided reaction products of phenol and non-conjugated aliphaticpolyunsaturated hydrocarbons having sites of unsaturation separated byat least two carbon atoms. A process for preparing these products isalso within the invention. The products of the invention are useful inthe preparation of resins and high polymers, in applications requiringresins and molding compounds, and the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The non-conjugated aliphaticpolyunsaturated hydrocarbon of the invention (short designation NAPH)can be cyclic or open-chain. NAPH is distinguished by the number ofcarbon atoms it contains, by the sites of unsaturation, and by beingfree of tertiary double bonds. These compounds contain from 7 to 21carbon atoms in the main structure. The unsaturation sites are partiallydependent on the configuration of NAPH. When NAPH is cyclic, 2 or morecarbon atoms are between the carbonto-carbon double bonds to make theproduct useful. However, when NAPH is open-chain, 3 or more carbon atomsare present between the carbon-to-carbon double bonds. Fewer interveningcarbon atoms than those mentioned above may result in the formation ofcompounds which are not the products of the invention. The points ofunsaturation may be unsymmetrical in respect to each other point ofunsaturation, provided the requisite carbon spacing between sites ofunsaturation is maintained. The maximum amount of unsaturation in NAPHis limited by the 3,644,533 Patented Feb. 22, 1972 ice C H where mequals 7 to 21 C H where q equals 12 to 21 C H where v equals 17 to 21and non-substituted cycloaliphatic compounds of the formula:

(C H where n equals 3 to 5 C H where y equals 8 to 21 C H where x equals12 to 21 C H where w equals 16 to 21 It is within the scope of thisinvention that the NAPH may be halogenated or substituted with suchgroups as methyl, ethyl or phenyl. Furthermore, cis and trans conligurations of NAPH may be used alone or in combination, in addition toother isomeric variations of the same compound.

Especially useful are NAPH such as those (a) based on or derivable frombutadiene, such as 1,5-cyclooctadiene, 1,5,9 cyclododecatriene, 1,5,9,13cyclohexadecatetraene, 1,5 dichloro 1,5 cyclooctadiene, and (b) otherssuch as 4-methyl-l,7-octadiene, 1,7-octadiene, 1,9- decadiene,1,13-tetradecadiene and 1,11-dodecadiene.

Examples of phenols which may be used in practicing the inventioninclude phenol itself or substituted phenols 0f the formula:

where R may be H, F, Cl, Br or a suitable substituent selected from thefollowing:

(a) Alkyl groups of 1 to 18 carbon atoms in any of their isomeric formsand substituted on the phenolic nucleus in the ortho, meta or parapositions;

(b) Alicyclic groups of 5 to 18 carbon atoms, e.g., cyclohexyl,cyclopentyl, methyl cyclohexyl, butyl cyclohexyl;

(c) Aromatic or alkyl groups of 6 to 18 carbon atoms,

e.g., phenyl, alpha-methyl benzyl, benzyl, cumyl;

(d) Alkyl, alicyclic, aryl and aralkyl ketones wherein the hydrocarbonis defined as hereinbefore; and

(e) Alkyl, alicyclic, aryl and aralkyl carboxylic groups wherein thehydrocarbon is defined as hereinbefore.

Suitable substituted phenols include the following: resorcinol,hydroquinone, para-tertiary-butylphenol, parasecondary-butylphenol,para-tertiary hexylphenol, paraisooctyl-phenol, para-phenylphenol,para-benzylphenol, para-cyclohexylphenol, para-decylphenol,para-dodecylphenol, para tetradecylphenol, para octa decylphenol,para-nonylphenol, para-cresol, para-beta-naphthylphenol,para-alpha-naphthylphenol, para-pentadecylphenol, paracetylphenol,para-cumylphenol, para-hydroxy acetophenone, para-hydroxy benzophenone,as well as the corresponding ortho and meta derivatives such asmeta-butylphenol, meta-cresol and ortho-butylphenol, as well as mixturesthereof.

The pure refined phenols may be used, but this is not always necessary.For instance, the phenols may be alkylated and then reacted with anolefin as a crude prod- 3 uct which may contain some polyalkylated aswell as unalkylated phenols. Mixtures of phenols mentioned herein mayalso be used.

From the foregoing, it is apparent that a wide variety of monophenolsmay be used in practicing the present invention provided that the phenolemployed is sufiiciently active to be capable of reacting with the NAPHof this invention. The choice of position substitution is important whenthe novolac type of resin is prepared. The metasubstituted phenol hasthre reactive positions and may be utilised to form novalacs which arecapable of being transformed into hard, insoluble and infusiblematerials by the addition of a methylene donor and the application ofheat. On the other hand, ortho and para substituted phenols generallyyield novolac-type resins which remain thermoplastic.

In addition to the above-mentioned phenol, disubstituted meta phenolsmay be used in the practice of this invention, if so desired.

The reaction products of the above-described NAPH and phenols may bebroadly classified as phenols, ethers, and mixed phenol ethers. All ofthe foregoing reaction products are prepared by the same preferredprocess, variations being made as to reaction conditions for theproduction of the one preferred class of reaction products. Whilecharging the desired amount of phenol to the reaction vessel the desiredamount of catalyst is added and stirred until well dispersed. Thereafterthe resulting solu tion or mixture is heated and the NAPH is graduallyadded over a predetermined period of time. The heating is then continuedfor an additional period of time to insure that the reaction is advancedto the desired degree of completion. Thereafter the reaction mixture isneutralized and the unreacted phenol and resulting water, if any, aredistilled 01f under vacuum. The reaction products are then ready forpurification and separation.

The suitable catalyst for use in the foregoing process are acidcatalysts. Among the more useful catalyst are boron trifiuoride andsulfuric acid. Additional useful catalysts include phosphoric acid,aluminum phenate, aluminum chloride, Friedel-Craft class catalysts andacidic ion exchange resins. Catalysts employed to prepare the productsof this invention are generally utilised in amounts up to about 5percent of the phenol charged. Small amounts of catalysts, that is,about one-tenth of one percent may be employed when the desired reactionproducts are the ether type product. It is preferable that from aboutonehalf percent to about 3 /2 percent of acid catalysts should bepresent when the desired reaction products are to be phenolic in nature.Upon the completion of the desired reaction the catalyst may beneutralised by charging to the reaction mixture a suitable neutralisingagent, such as a slurry of lime, sodium bicarbonate, calcium bicarbonateor an alkali such as sodium hydroxide in solution.

The inventive reaction products may be prepared at temperatures rangingfrom less than ambient room temperatures that is about degreescentigrade to about 250 degrees centigrade. However, the reactiontemperature will not usually exceed about 200 degrees centigrade and itshould usually be greater than degrees centigrade. Very mild reactionconditions are desirable for the formation of the ethers of thisapplication. The temperature employed should be less than about 50degrees centigrade and may be as low as 10 degrees centigrade but it ispreferable that the reaction temperature be from about 20 degrees toabout degrees centigrade. The phenols of this invention are bestprepared by employing temperatures from about degrees to about 170degrees centigrade.

The reaction products of phenols and NAPH may be broadly classified asphenols, ethers or phenolic ethers and may then be further sub-dividedinto mono-phenols, bisphenol, novolacs, mono-ethers, di-ethers and mixedphenol ethers. Preparation of each of the broad classes of materials,that is, ethers and phenols, is dependent upon temperature and catalystconditions in the reaction vessel. Additionally, the preparation of thevarious sub-classes depends upon the ratios of reactants charged to thereaction vessel. These ratios, when stated in terms of the amount ofphenol employed, result in the products as follows:

(a) mono-phenols and mono-ethers result when the molar ratio issubstantially 1: 1;

(b) bisphenols, diethers and mixed phenol ethers result when at leastabout two or more moles of phenol are charged per mole of NAPH;

(c) novolac type resins are made with a slight molar excess of phenol,i.e., at least about 10 mole percent; and generally up to about molepercent, and when the reaction is sustained at high temperatures for asuitable time.

It is believed that the reaction products formed when equal moles ofphenol and cyclic NAPH are reacted undergo a structural change. Theaddition reaction is that which normally follows from the reaction of ahydrogen donor compound with an unsaturated compound. At the completionof this reaction there should he places of unsaturation remaining sinceeach NAPH has two or more points of unsaturation and only one isutilized in the reaction of one mole of phenol, however, brominationstudies have not disclosed any ethylenic unsaturation in the product.Instead, these studies indicate that substantially all of the brominewhich is consumed by the reaction product is consumed on a substitutionbasis and suggests that the resulting phenols and ethers have inaddition to the phenol ring, a polycyclic structure adjoining. Probablestructures are as follows. (The phenol is described previously):

(a) the reaction products of phenol and 1,5-cyclo octadiene R I- I I CUand (b) the reaction products of phenol and 1,5,9- cyclodecyltriene Incontract with the cyclic NAPHs discussed above, the linear NAPHs retaintheir characteristic structure and undergo the addition reaction. Atypical reaction is the equimolar reaction of phenol with 1,7-octadieneto yield A second isomer of these compounds may also be obtained bysubstitution on the first carbon of 1,7-octadiene.

The reaction of two moles of phenol with one mole of NAPH results inproducts which may be broadly described in bisphenols, ethers, and mixedether-phenolics. In the case where the cyclic NAPH is a triene thereaction product additionally undergoes a rearrangement as evidenced bythe substitution of bromine when the product is subject to bromination.When the reactions are phenol and 1,5-cyclooctadiene the followingproducts are obtained, depending on the reaction conditions employed.While both the 1,5 and 1,6 cyclooctane isomers may be prepared forconvenience only the 1,5 isomer is shown below.

polycyclic structure as indicated by formulas below.

Again, for convenience, it is sufficient to show one isomer.

The reaction products of this invention also include novolac-like resinswhich result from the gradual addition of the desired NAPH to phenolunder conditions similar to that used in the preparation of bisphenolsof this inven- 40 tion. Those novolacs are permanently fusible resins,containing up to about 20 phenolic nuclei. Very useful novolacs areprepared which contain from three to about seven repeating phenolicnuclei in the reaction products. It is to r be appreciated that when thephenol is phenol itself, then the resulting novolac may contain branchedstructures. However, these branched structures have the characteristicsof the linear novolac with respect to fusibility and solubility. Thenovolacs, with the addition of methylene donors such ashexamethylenetetramine, and the application of heat will set to be ahard insoluble, infusible plastic material. Typical novolacs prepared bythis process include the reaction products of phenol and 1,5-cyclooctathe novolac which is the reaction product of phenols and 1,7octadiene I on CH3 9H3 i711: (3113 l t-r-rrrr ff tri H2 H2 H2 H2 H2 H2H2 H2 H2 H; H R

m=1 to 20 and the novolac which is the reaction product of phenols and1,5,9-cyclododecy1triene:

Similar phenols, bisphenols and novolacs result when other NAPH membersare reacted with phenol in the process of this invention.

A carbon-to-carbon double bond is to be expected in the eight memberring of the one to one molecular condensates. By the same rationalscarbon-to-carbon double bonds are expected to be in the twelve memberring when 1 and 2 moles of phenol are condensed with one mole of NAPH.The presence of a double bond is demonstratable by the addition ofbromine, following the method of P. C. Mcllhiney, Journal AmericanChemical Society vol. 16, page 275. For results of this analysis, seetable below:

TA'BLE.BROMINATION The equal molecular compounds of phenol and NAPH maybe used as either the end products or as an inter- OFPHENOL-CYCLOOCTADIENE PRODUCTS Atoms bromine Moles excess Time consumedMoles HBr Atoms Br Br reacted, per mole formed added per formed hoursphenol per mole mole per mole Sample:

o-Monophenol 20 9. 27 5, 18 p-Monophenol- 20 8. 42 4. 69 D 19 7. 43 4.Do- 1.5 5. 94 3. 28 D0 0.5 5.41 3. 02 Phenol ether 3 5. 14 2, 81 Phenolether and monophenols. 3 7. 28 3. 74 Monophenol from dibromocyclooctanes 4 3. 59 1. 72 Cyclododocatriene reaction product (list. 175185 C. at 05 mm. mercury 3. 82 1. 0. 02 Cyclododocatriene reaction product dist.,residue 20 6. 28 2. 86 0. 57 Comparative:

Cashew nut oil 24 8- 2 1. 88 3-4. 3 Cyclooctadiene- 2 3. 89 0. 28 3. 33Phenol 2 3 2.18 0.02 Blank 2 Meg. Br-9.12, found 9.20 meg., HBr found0.01

In only a few instances is there evidence of bromine addition, and evenhere the amount added was insignificant.

All available evidence indicates that the double bond expected is notpresent. The validity of the bromine method of analysis is substantiatedby applying it to the phenol itself and to a cashew shell oil phenolcontaining an unsaturated side chain. No unsaturation was found inphenol while cashew shell oil showed the presence of the expected doublebonds. Furthermore, the infrared spectra of the products do not have aband attributable to the normal carbon double-bond absorption.

An alternative route to the phenolcyclooctadiene condensates is byaddition of hydrobromic acid to the cyclooctadiene to givedibromocyclooctane. Good yields are obtained in this step. Thereafterthe dibromocyclooctane was reacted with an excess of phenol using ferricchloride as a catalyst in the expectation of forming a bisphenol. Upondistillation of the reaction mixture, 2. fraction having boiling pointbetween degrees to 240 degrees Centigrade at 0.25 mm. of mercury wasobtained, which contained the desired bisphenol. Additionally, apolycyclic monophenol without ethylenic unsaturation was also formed.The monophenol has similar properties to that obtained by the directaddition of phenol to cyclooctadiene. Substantially the same resultshave been obtained when the polyolefin is cyclododecatriene.

used as intermediates or as final end products. These phenolic resinsmay also be esterified with di-basic acids or their derivatives such asthe anhydrides or acid halides to form new polyester plastics which,because of the cycloalphatic residues present, have unusually goodelectrical properties. As a final end product, these resins all becomeheat hardenable when mixed with hexamethylenetetramine or othermethylene donors.

Useful phenolic resins may be prepared from the novolacs describedabove. The novolac is ground to the desired particle size and thedesired amount of methylene linked donor material such ashexamethylenetetramine is admixed. The basic resin is now ready for usein molding compounds and varnishes. However, modification of the basicresin may be made by admixing, either singularly or in combination,fillers and novolacs prepared by the reaction of phenols and aldehydes.

The use of fillers with the compounds in this invention is optional anddependent upon the final properties desired in the article being molded.Such fillers may include one or more of the following: glass, quarts,mica, woodflour, asbestos, cellulose, graphite, coloring matter andothers. The Technology of Plastic and Resins, Mason, J. P. and ManningJ. F. Van Nostrand Company (1945) at p. 396 et seq. describes otherfillers and reasons for their employment, such as to change densities orthe chemical resistance of phenolic resins.

The practice of this invention is illustrated by but not limited to theexamples given below which describe preferred forms thereof. All partsare by weight and all temperatures are in degrees centigrade unlessotherwise stated.

EXAMPLE 1 Preparation of solid monophenol from cyclooctadiene EXAMPLE 4Preparation of liquid monophenol from cyclooctadiene A reaction productprepared from phenol and 1,5- cyclooctadiene by a procedure similar tothat described in Example 1 was subjected to vacuum distillation whichyielded 141.5 grams of a liquid boiling from 143-153 degrees at 1.5 mm.of mercury. To this Were added 600 grams of 10 percent aqueous NaOH. Oncooling and standing overnight a precipitate formed (sodium salt of thesolid monophenol). About 2 liters of acetone were added and the solidprecipitate was filtered ofi and set aside. Acetone was removed from thefiltrate by distillation and theremaining aqueous residue was extractedwith ether yielding 68 grams of light brown oil. Fractional distillationthrough an 18 x /2 packed column yielded the following cuts.

1 Hereafter referred to as liquid monophenol.

to 150 degrees at mm. of mercury pressure. The vapor temperature went to105 degrees. The crude product obtained was weighed (136 grams),transferred to a smaller pot and distilled under vacuum. A fractionboiling at 160- 174 degrees at 3 mm. of mercury was collected (65 grams)which partially crystallized on standing. Recrystallization frompetroleum ether (3 times) resulted in a colorless crystalline material(M.P. 106-109 degrees) having the following analysis:

Calculated for C H .C H OH (percent): OH, 8.4; C, 83.2; H, 8.9. Found(percent): OH, 8.36; C, 82.8; H, 9.5.

The infrared spectrum of this solid monophenol showed no absorptioncharacteristic of an ethylenic bond. The spectrum also indicatedmonosubstitution of the phenol in the para position. On bromination inC01; solution for 20 hours by the method of McIlhiney 8.32-8.42 atoms ofBr were absorbed per mole of the phenol and 4.69-4.88 moles of HBr wereliberated, indicating that bromine reacted by substitution rather thanby addition at an ethylenic bond.

EXAMPLE 2 Preparation of monophenol from cyclooctadienehighertemperature cyclooctadiene-1,5 (54 grams) was added dropwise during 65minutes to a stirred mixture of phenol (1000 grams and BF grams) at146-155 degrees. After an additional 2 hours, at 150 degrees thereaction mixture was cooled and worked up as in Example 1. Themonophenol fraction boiling at 143-153 degrees at 1 mm. of mercurypressure weighed 61 grams.

EXAMPLE 3 Preparation of monophenol from cyclooctadiene lower mole ratioCyclooctadiene-l,5 (108 g., 1.0 m.) was added dropwise to a stirredmixture of phenol (141 g., 1.5 m.) and BE; (2.8 g.) during 90 minutes.The temperature was 92-100 degrees. Heating at 100 degrees was continuedfor an additional four and one-half hours. Work up of the reactionmixture was as in Example 1. The monophenol fraction boiling at 160-185degrees at 5 mm. of mercury pressure weighed 70 grams.

The hydroxyl contents of Cuts 3, 4 and 5 (7 .898.31%) show that theseare monophenols of the general formula C H -C H OH formed by the unionof one molecule each of cyclooctadiene and phenol. The infrared spectrumof the liquid monophenol indicated it to be a monosubstituted phenolwith an orthosubstitutent and to contain no ethylenic bond. Brominationof the liquid monophenol in CCL; solution for 20 hours by the sameprocedure used with the solid monophenol in Example 1 also failed toreveal double bonds. A total of 9.27 atoms of bromine were consumed permolecule of phenol but 5.18 moles of HBr were liberated.

The liquid monophenol was also converted to an N- methyl carbamate byreaction with stoichiometric proportions of N-methyl carbamyl chlorideand triethylamine. After three recrystallisations from petroleum etherthe derivative melted at 8991.5 degrees and contained 5.5 percent N(theory for C H C H OCONHCH 5.4% N).

The liquid monophenol is considerably more soluble in aqueous alkalithan the solid monophenol. From the material precipitated by treatmentwith 10 percent aqueous caustic as mentioned above there were recoveredby neutralisation and crystallisation from petroleum ether 32 grams ofsolid monophenol having MP. of -106 degrees.

Both the liquid monophenol and the solid monophenol of Example 1 hardenwhen heated with hexamethylenetetramine or paraformaldehyde and acid oralkaline catalysts but do not become insoluble in organic solvents.

EXAMPLE 5 Preparation of phenolic resins from cyclooctadiene The highboiling residues obtained in Example 1 were further heated to 270degrees under 1 mm. pressure to complete removal of the monophenol. Theproduct was a permanently fusible red resin which was brittle when cold.On pulverization and mixing with about 10 percent of its own weight ofpulverized hexamethylenetetramine the resin cured rapidly at degrees toyield a hard insoluble mass. The resin was also rendered thermosettingby mixing with paraformaldehyde and acid or basic catalysts. The uncuredresin was also somewhat soluble in toluene. Extraction of it with about25 times its own weight of toluene yielded a soluble product which con-1 1 tained C, 80.9% and H, 8.4% while the undissolved high meltingresidue contained C, 82.0% and H, 8.7%. A bisphenol of the formula HOC'H -C H -C H OH would contain C, 81.1% and H, 8.1% while a resin of thegeneral formula HO6H4 OBI-I14 CsHgOH C8H14 CH4OH would contain C, 81.9%and H, 8.4%. The insoluble material cured readily withhexamethylenetetramine or paraformaldehyde at about 165 degrees.

Molding compounds of excellent dielectric strength may be prepared bycompounding the above fusible resin with hexamethylenetetramine,woodrfiour or mica filler, color, wax, etc. as is customarily done withphenol-formaldehyde novolacs.

EXAMPLE 6 Preparation of phenolic ether from cyclootadiene Phenol'andcyclootadiene were reacted as in Example 1 except that the amount of BFcatalyst was reduced from 18 grams to 1 gram and the reaction time wascut to 4 /2 hours at 34-41 degrees. Distillation gave 20.6 grams ofproduct boiling from 98-113 degrees under 0.5 mm. of mercury. Thisproduct contained 2.1 percent OH (theory for the monophenol C H -C HOH-8.3%) indicating that it is largely an ether of the type C H OC H Onbromination, as in Example 1, it gave no evidence of unsaturation,5.14-5.2 atoms of Br being absorbed and 2.81-2.83 moles of HBr beingliberated. The infrared absorption spectrum also revealed no ethylenicunsaturation.

EXAMPLE 7 Preparation of phenolic ether from cyclooctadieneCyclooctadiene-1,5 (54 grams 0.5 moles) and BF (0.5 gram) were dissolvedin 200 grams of n-hexane. To this solution, there were added dropwise 47grams (0.5 m.) of phenol during 60 minutes. The reaction medium wasmaintained at -35 degrees by means of an ice bath. After an additionalhour at room temperature, the catalyst was neutralized and the solventand unreacted phenol and cyclooctadiene were stripped 01f. The residuewas distilled under vacuum. A 22 g. fraction boiling at 104-106 degrees,at 0.5 mm. of mercury vacuum, was collected. This had a refractive indexof 1.5435 and a low hydroxyl content.

EXAMPLE 8 Preparation of monophenol from cis, trans,transcyclododecatriene 1,5,9-cyclododecatriene (cis, trans,trans-isomer), (53 grams or 0.33 mole) was added dropwise to a stirredmixture of phenol (3015 grams or 32 moles) and BE, (54 grams) maintainedat 90 degrees. After addition was complete the mixture was kept at 90degrees for 5 hours and was then vacuum distilled after neutralisationwith aqueous NaHCO A monophenol fraction (32 g.) boiling from 175-185degrees under 0.5 mm. of mercury was obtained. This contained 6.74% OH(calculated for the monophenol C fl .C H OH6.75% OH). The infraredspectrum of the material gave no indication of the presence of ethylenicbonds. On bromination for 20 hours by the method of Example 1, 3.82-4.74atoms of Br were absorbed per mole of monophenol and 1.90-2.33 moles ofHBr were liberated. These results indicate that the compound has formedby the addition of one mole of phenol to one double bond of the cyclicolefin and by the loss of the remaining two double bonds in cyclisationreactions.

The carbamate of this phenol, prepared by the general procedure ofExample 4, is highly effective as an agent for the control of foliarblight. The phenol hardens when heated with hexamethylenetetramine,paraformaldehyde, acid or alkaline catalysts but does not becomeinsoluble in organic solvents.

EXAMPLE 9 Preparation of phenolic resin from cis, trans,transcyclododecatriene The residue remaining after distilling off themonophenol of Example 8 was subjected to further heat and vacuumtreatment to complete the removal of the monophenol. Material boilingbelow 210 degrees at 0.5 mm. of mercury was removed and 38.5 grams of apermanently fusible resin were obtained as a residue. This materialresembled the resin of Example 5 and cured to a hard, insoluble masswhen mixed with hexamethylenetetramine or paraformaldehyde and catalystand heated to 165 degrees. Like the product of Example 5 it may be usedto prepare thermosetting molding compounds having good luster anddielectric strength.

EXAMPLE 10 Preparation of monophenol and phenolic resin from trans,trans, trans-cyclododecatriene Using a procedure like that of Examples 8and 9 the trans, trans, trans-isomer of 1,5,9-cyclododecatriene wasreacted with phenol and the monophenol and phenolic resin recovered asbefore. These products were very similar to those obtained in Examples 8and 9, the only difference noted being a slight difference in theinfrared spectrum of the monophenol fraction boiling from 175-185degrees under 0.5 mm. of mercury. The similarity between the productsobtained from the cyclododecatriene isomers appears to be due to theloss of the ethylenic unsaturation responsible for the cis, transisomerism of cyclododecatriene.

EXAMPLE 11 Preparation of a bisphenol from cyclooctadienecyclooctadiene-1,5 (54 grams 0.5 m) was added dropwise during 55 minutesto a stirred mixture of phenol (1000 grams) and BF (18 grams) at 97-100degrees. After an additional 5 /2 hours at 100 degrees, the product wasworked up as in Example 1. A monophenol fraction, boiling at 150-158degrees, at 2 mm. of mercury pressure and weighing 61 grams, wasobtained. The pressure was reduced to 0.4 mm. of mercury, and abisphenol fraction, boiling at 200-245 degrees was collected. This was ared, viscous liquid having a hydroxyl content of 9.2 percent. The crudebisphenol fraction thus obtained contains an ethereal component, becausea bisphenol of the general formula HOC H .C H .C H OH would contain 11.5percent OH.

EXAMPLE 12 Preparation of a bisphenol from cyclooctadiene The materialremaining after distilling off the phenolic ether and monophenol ofExample 6 was subjected to a. further distillation. A fraction boilingat 225-245 degrees at 0.5 mm. of mercury pressure was collected. Thisweighed 25 grams and was red viscous liquid. It had a hydroxyl contentof 8.62 percent.

EXAMPLE 13 Preparation of bisphenol [di(hydroxyphenyl)octane] andmonophenol from 1,7-octadiene To a mixture of 470 grams phenol and 12grams BR at degrees there were added dropwise during 60 minutes, 27.6grams of 1,7-0ctadiene. After an additional hour at 60-70 degrees, themixture was cooled to 40 degrees and washed with a saturated aqueoussolution of NaHCO- and then with water. After distilling off thedissolved water and phenol, there were obtained grams of viscous lightcolored fluid. This was then distilled under vacuum. A monophenolfraction boiling at -120 degrees at .25 mm. of mercury was obtained.This product weighed 11.4 grams and had a hydroxyl content of 7.8percent. A monophenol of the type HOC H C H has a hydroxyl content of8.3 percent.

13 The bisphenol fraction weighed 31.4 grams and distilled over at190-201 degrees at .4 mm. of mercury vacuum. It was a viscous paleyellow colored liquid with a hydroxyl content of 11.1 percent. Abisphenol of the type has a hydroxyl content of 11.38 percent. The stillbottoms weighed 7.8 grams. This was a hard, brittle phenolic resin witha hydroxyl content of 8.8 percent. The bisphenol and the phenolic resincured at 165 degrees when mixed with '10 percent of their own weight ofhexamethylenetetramine. The cured resins were tough, insoluble materialshaving outstanding flexibility while hot. They were also surprisinglyresistant to discoloration at elevated temperatures.

Various changes and modifications may be made and equivalents may besubstituted in the method and composition of this invention, certainpreferred forms which have been herein described, without departing fromthe scope of this invention. Such modifications are to be regarded aswithin the scope of the invention.

We claim:

1. A product of the acid catalyzed reaction of substantially equivalentmolar proportions of phenol and a compound selected from the groupconsisting of 1,5-cyclooctadiene, 1,5,9-cyclododecatriene,1,5,9,13-cyclohexadecatetraene, 1,5-dichloro-l,S-cyclooctadiene,4-methyl-l,7- octadiene-l,7-octadine, 1,9-decadiene, 1,13-tetradecadieneand 1,11-dodecadiene conducted at a temperature of from about 10 up toabout 250 degrees centigrade.

2. A product according to claim 1 wherein the compound is1,5-cyclooctadiene.

3. A product according to claim 1 wherein the compound is1,5,9-cyclododecatriene.

4. A product according to claim 1 wherein the compound is 1,7-octadiene.

References Cited UNITED STATES PATENTS 6/1943 Pratt 260619 5/1951 Pineset a1. 260624 OTHER REFERENCES BERNARD HELFIN, Primary Examiner US. Cl.X.R.

Cross references adequately provided by parent patent No. 3,539,646.

